Sulfonate-containing photopolymer systems

ABSTRACT

An isocyanate-terminated sulfocompound is the reaction product of a polyisocyanate and a sulfopolyol or sulfopolyamine which is the reaction product of one mole of a sulfodicarboxylic acid and about two moles of an aliphatic polyol or polyamine having two or more hydroxyl or amino groups attached to a linear chain and having a molecular weight of up to 2000. The sulfocompound can be reacted with ethylenically-unsaturated alcohols, water, polyamines, or polyols, to give ethylenically-unsaturated sulfocompounds, sulfopolyureas or sulfopolyurethanes.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 009,616 filed 1/22/87 nowU.S. Pat. No. 4,746,717, which is ia continuation of application Ser.No. 739,542 filed 5/30/85 now abandoned which is a continuation-in-partof application Ser. No. 562,459 filed 12/16/83 now U.S. Pat. No.4,558,149.

TECHNICAL FIELD

This invention relates to a water- and organic solvent-soluble compoundwhich is an ethylenically-unsaturated derivative of a sulfopolyol orsuflopolyamine which on exposure to energy is converted to a water- andorganic solvent-insoluble polymer. In another aspect, the inventionrelates to a substrate bearing a layer of water and solvent-solublesulfocompound. In a further aspect, the invention relates to a substratebearing a layer of the polymer of the sulfocompound. In a still furtheraspect the invention relates to isocyanate-terminated sulfocompoundsfrom which the ethylenically-unsaturated derivatives are prepared.

BACKGROUND ART

Water-soluble polyesters which are curable to insoluble resins onexposure to heat or radiation are known. U.S. Pat. No. 2,845,402discloses polyesters that on heating in the presence of a catalyst cureto insoluble resins and that are the reaction products ofpolyalkyleneoxide polyols and dicarboxylic acids. U.S. Pat. No.4,073,777 discloses polyesters and polyesteramides that crosslink towater-insoluble resins on exposure to radiation and that are thereaction products of (1) at least one dicarboxylic acid, (2) at leastone glycol, (3) sufficient sulfoaromatic dicarboxylic acid, dihydroxy,or diamino compound to provide water dispersibility to the reactionproduct, and (4) an unsaturated mono or dicarboxylic acid.

The water-soluble polyesters described in the above cited patents,although convertible on exposure to actinic radiation to water-insolubleresins, are high molecular weight compounds that are prepared by hightemperature reactions requiring the heating of unsaturated reactants totemperatures of about 270° C. for long periods of time. Such highmolecular weight compounds have a high melt viscosity that adds to thedifficulties encountered in handling the compounds. Also, because of theharsh and prolonged heating required in their preparation, the ethylenicunsaturation does not always survive.

SUMMARY OF THE INVENTION

The present invention provides a low molecular weight (i.e., generallyless than 6500), film-forming, polymerizable, ethylenically-unsaturatedsulfocompound that is hydrophilic and solvent-dispersible (i.e., solubleor dispersible in both water and organic solvents) but is readilyconverted on exposure to actinic radiation to a polymer that issolvent-insoluble (i.e., not soluble in water, organic solvents, ormixtures of water and organic solvents) and, in certain examples, ishydrophobic.

Briefly, the sulfocompound is the poly(ethylenically-unsaturated) ester,amide, urethane, or urea that comprises either (1) the reaction productof a polyether or polyester sulfopolyol or sulfopolyamine and anethylenically-unsaturated compound selected from 2-alkenylazlactones andethylenically-unsaturated isocyanates or (2) the reaction product of anisocyanate group terminated sulfopolyether or sulfopolyester and anethylenically unsaturated alcohol, the sulfopolyol or sulfopolyaminecomprising the reaction product of one mole of a sulfodicarboxylic acidand two moles of an aliphatic polyether- or polyester- polyol orpolyamine having a molecular weight of up to about 2000 and two to fourhydroxyl or amino groups and the ethylenically-unsaturated sulfocompoundhaving an ethylenic unsaturated functionality of 2 to 18 and anequivalent weight per ethylenic unsaturated functionality of less than2500.

DETAILED DESCRIPTION OF THE INVENTION

Preferably, the ethylenically-unsaturated sulfocompound of the inventioncomprises the reaction product

1. a sulfopolyol or a sulfopolyamine which is the reaction product of

(a) one mole of a sulfodicarboxylic acid and

(b) about two moles (i.e., 1.95 to 2.05 moles) of one or more aliphaticpolyether- or polyester polyols or polyamines (i.e., a compound in whichthe structure to which two or more hydroxyl or amine groups are attachedis a saturated linear chain of up to about 110 carbon atoms in units of2 to 12 --CH₂ -- groups which can be separated by individual oxygenatoms and ##STR1## the polyol and polyamine having a molecular weight ofup to about 2000 and (c+1) hydroxyl or amino groups (in which c is aninteger of 1, 2, or 3); and

2. 2 c moles of either (a), (b), or (c), in which

(a) is a compound selected from

(i) 2-alkenylazlactones having the formula ##STR2## wherein R ishydrogen or methyl;

R¹ is a covalent bond, --CH₂ -- or --CH₂ CH₂ --,

R² and R³ are independently hydrogen or methyl; and

(ii) ethylenically-unsaturated isocyanates having the formula ##STR3##wherein R⁴ is a covalent bond, ##STR4## wherein R⁵ is a linear orbranched chain of 1 to 12 carbon atoms optionally containing onenonperoxidic catenary oxygen atom or ##STR5## or R⁵ is a 5- or6-membered carbocyclic group optionally substituted by lower alkylgroups having 1 to 4 carbon atoms, the carbocyclic group having a totalof up to 12 carbon atoms, and

R⁶ is an organic group selected from linear or branched alkylene groupshaving 2 to 12 carbon atoms, a cyclopentamethylene group, acyclohexamethylene group, a 5- or 6-membered azacyclic group, aphenylene group, a naphthalne group, a phenylenemethylene phenylenegroup, the organic group optionally substituted by up to four loweralkyl groups having 1 to 4 carbon atoms and a total of up to 15 carbonatoms; or

(b) one or more polyisocyanates or their dimerization and theirtrimerization products having the formula

    OCN--R.sup.12 --NCO).sub.d                                 III

wherein R¹² is an organic group having a valence of d+1 selected fromlinear and branched groups having 2 to 12 carbon atoms, 5- and6-membered carbocyclic groups having 5 to 14 carbon atoms, and d is anumber having a value of 1 to 3, the reaction product of the sulfopolyolor polyamine and the polyisocyanate comprising an isocyanate-terminatedsulfocompound having the formula: ##STR6## wherein

R⁹ is an arenetriyl group (trivalent arene group) having 6 to 20 carbonatoms or an alkanetriyl (trivalent alkane) group having 2 to 20 carbonatoms remaining after the removal of carboxyl and sulfo groups fromsulfoarene- and sulfoalkane dicarboxylic acids having the formula##STR7## in which M is a cation, and preferably M is Na, but M can be H,an alkali metal ion such as K or Li, an alkaline earth metal cation(e.g., Mg, Ca, or Ba), or a primary, secondary, tertiary, or quaternaryammonium cation such as ammonium, methylammonium, butylammonium,diethylammonium, triethylammonium, tetraethylammonium, and benzyltrimethylammonium cation;

R¹⁰ is a linear aliphatic group having a valence of (c+1) that is theresidue of a polyether or polyester polyol or polyamine having theformula

    HXR.sup.10 (XH).sub.c                                      X

the aliphatic group consisting of a saturated chain of up to about 110carbon atoms in units of 2 to 12 --CH₂ -- groups which can be separatedby individual oxygen atoms and ##STR8## the aliphatic group having amolecular weight of up to about 2000, wherein c is an integer of 1, 2,3;

each X is independently --O-- or --NH--; and

R¹² and d are as defined above for Formula III; theisocyanate-terminated sulfocompound then being reacted with 2 c·d molesof an ethylenically-unsaturated alcohol having the formula ##STR9##wherein

R is as defined above for Formula I;

R⁷ is a ##STR10##

R⁸ is a polyvalent aliphatic group selected from linear and branchedalkyl groups having a valence of (a+1), 2 to 12 carbon atoms, that canbe interrupted by one nonperoxidic catenary oxygen atom, and/or one##STR11## and alicyclic groups having a 5- or 6-atom carbocyclicstructure optionally substituted by up to 4 lower alkyl groups having 1to 4 carbon atoms and a total of up to 12 carbon atoms, and preferablythe polyvalent group is selected from ##STR12## in which e is an integerof 1 to 6 inclusively; and

a is an integer of 1, 2, or 3; or

(c) the reaction product of one mole of organic polyisocyanate ofFormula III and d moles of an ethylenically-unsaturated alcohol ofFormula IV;

there being essentially no (i.e., less than 0.5 weight percent)hydroxyl, amino, or isocyanate groups remaining after the reaction of 1.with either (2a), (2b), or (2c).

In step 2b, an excess of polyisocyanate of Formula III can be used inthe reaction with the sulfopolyol or sulfopolyamine in an amount up toabout 100% excess (e.g., up to about four moles of polyisocyanate permole of sulfopolyol or sulfopolyamine). When such an excess is used theisocyanate-terminated sulfocompound of Formula IX mixed with excesspolyisocyanate is obtained. This mixture can then be used to provide theethylenically unsaturated sulfocompound by reaction with one mole ofethylenically-unsaturated alcohol of Formula IV per equivalent ofisocyanate present in the reaction mixture of the isocyanate-terminatedsulfocompound. A mixture of the ethylenically-unsaturated sulfocompoundand non-sulfocompound containing ethylenically-unsaturated compounds isobtained.

The various chemical reactions that provide the sulfocompounds of theinvention and their derivatives are shown in the FLOW CHART below.##STR13##

Preferably, the low molecular weight, film-forming, polymerizable,ethylenically-unsaturated sulfocompound has an equivalent weight perethylenic unsaturated functionality of about 300 to 1000. As theunsaturated functionality is increased above about 600, the polymerbecomes increasingly hydrophilic and as the functionality is decreasedbelow about 600, the polymer becomes increasingly hydrophobic.

There is also provided by the invention energy curable coatingcompositions comprising the hydrophilic, water- and organicsolvent-dispersible, polymerizable, ethylenically-unsaturatedsulfocompound in a solvent (preferably water), and optionally a freeradical source. Furthermore, there are provided substrates bearing alayer comprising the preferable hydrophilic, water- and organicsolvent-soluble polymerizable ethylenically-unsaturated sulfocompound ofa sulfopolyester polyol or polyamine and, also, substrates bearing alayer of the polymerized ethylenically-unsaturated sulfocompound of asulfopolyester polyol or polyamine.

As used in this application:

"poly(ethylenically-unsaturated ester or amide)" means an organiccompound having an ethylenically-unsaturated group (i.e., H₂ C═CH-- orH₂ C═C(CH₃)--) that is connected to the compound by means of at leastone of a bond, a methylenene group, a carboxylate ##STR14## or acarbamate group (also called urethane group, i.e., ##STR15##

"low molecular weight ester" means a compound that is theethylenically-unsaturated derivative of a sulfoester that is thereaction product of one mole of a sulfodicarboxylic acid and no morethan two moles of polyo or polyamine having 2 to 4 hydroxyl or aminogroups followed by reaction with 2 to 6 moles of anethylenically-unsaturated compound. The compound therefore, has only onesulfo group and generally has a molecular weight of less than 6500, andpreferably less than 4000;

"lower alkyl" means 1 to 4 carbon atoms;

"catenary" means in the main chain or backbone and not in a pendent orterminal group;

"sulfo" means a --SO₃ H group or a salt thereof;

"sulfocompound" means a water- and organic solvent-soluble compoundwhich is an ethylenically-unsaturated derivative (i.e., an ester or anamide) of a sulfopolyol or sulfopolyamine;

"sulfopolyesterpolyurethane" or "sulfopolyoxyalkylenepolyurethane" or"sulfopolyurethane" means the reaction product of theisocyanate-terminated sulfocompound of Formula IX with a polyalcohol ofFormula ##STR16## and

"sulfopolyesterpolyurea" or "sulfopolyoxyalkylene-polyurea" or"sulfopolyurea" means the reaction product of the isocyanate- terminatedsulfocompound of Formula IX with water or a primary or secondarypolyamine to provide ##STR17##

The water- and organic solvent-dispersible, low molecular weight,film-forming, polymerizable, ethylenically-unsaturated sulfocompounds ofthe invention preferably have the general formulas ##STR18## wherein:

R, R⁷, R⁸, R⁹, R¹⁰, R¹², X, M, a, c, and d are defined above, and##STR19## R², R³, and R⁴ are as defined above.

The coating compositions of the invention are energy-curable andpreferably comprise the low molecular weight, solvent-soluble,film-forming, polymerizable urethane group-containing compounds ofFormulas VI and VII and a free radical generating compound thatgenerates free radicals on application of energy.

The low molecular weight, water- and organic solvent-dispersible,film-forming, polymerizable sulfocompound of the invention can beprepared by procedures well known in the art, preferably by the reactionof one mole of sulfoarene or sulfoalkane dicarboxylic acid, FormulavIII, (or their esters prepared from an alcohol of low molecular weight,i.e. below about 94, their acid anhydrides, or their acid halides) withtwo moles of aliphatic monomeric or polymeric polyol having (c+1)hydroxyl or amino groups forming a sulfopolyol or sulfopolyamine having2 c hydroxyl or amino groups, whether c is an integer of 1, 2, or 3. Thesulfopolyol or sulfopolyamine is then caused to react with either: (a)(i) 2 c moles of an ethenylazlactone, or (ii) with 2 c moles of anethylenically-unsaturated isocyanate, preferably an isocyanatoalkylacrylate or polyacrylate, (b) 2 c moles of an organic polyisocyanate toform an isocyanate-terminated sulfopolyol or sulfopolyamine that isfollowed by reaction with 2 c moles of an ethylenically-unsaturatedalcohol, preferably a hydroxyalkyl acrylate, or (c) 2 c moles of thereaction product of one mole of organic polyisocyanate with d moles ofan ethylenically-unsaturated alcohol, preferably a hydroxyalkylacrylate. As is known in the art, these reactions can be performed inthe presence of a mercury, lead or tin catalyst such as dibutyltindilaurate. Preferably, the catalyst is a tertiary amine, tricalciumaluminate, or the potassium salt of a molybdenum ester oftriethyleneglycol as is disclosed in U.S. Pat. No. 2,916,464. Thepreparation of the sulfopolyol or sulfopolyamine can be carried out byheating the reactants for about 2 to 20 hours, preferably 4 to 10 hours,at temperatures from 150° to 300° C., preferably 200° to 250° C., underreduced pressure or an inert atmosphere. Reactions in which one of thecomponents is an acrylic group-containing compound need be heated at atemperature of only about 20° to 100° C., preferably 30° to 60° C. for 1to 10 hours.

Aliphatic polyols, (HO)_(c) R¹⁰ --OH, useful in preparing the water- andorganic solvent-dispersible sulfocompounds of the invention have amolecular weight of 62 to 1000 and include, for example, monomeric andpolymeric polyols having two to four hydroxyl groups. Examples of themonomeric polyols include ethylene glycol, propylene glycol, butyleneglycol, hexamethylene glycol, 1,1,1-trimethylolpropane, pentaerythritol,and the like. Examples of polymeric polyols include the polyoxyalkylenepolyols, i.e., the diols, triols, and tetrols, the polyester diols,triols, and tetrols of organic dicarboxylic acids and polyhydricalcohols, and the polylactone diols, triols, and tetrols having amolecular weight of 106 to about 2000. Examples of polymeric polyolsinclude polyoxyethylene diols, triols and tetrols such as the Carbowax™polyols available from Union Carbide, the polyoxytetramethylenediolssuch as Polymeg™ polyols available from Quaker Oats Company, thepolyester polyols such as the Multron™ poly(ethyleneadipate)polyolsavailable from Mobay Chemical Company, and the polycaprolactone polyolssuch as the PCP™ polyols available from Union Carbide.

Aliphatic polyamines, (H₂ N)_(c) R¹⁰ --NH₂, useful in preparing thesulfocompounds of the invention are the 5 polyamines available fromJefferson Chemical Co., Inc., a subsidiary of Texaco, Inc., under thetradename Jeffamine™ such as Jeffamine™ D-400, a polyoxypropylenediamine having a molecular weight of about 400; Jeffamine™ D-230, apolyoxypropylene diamine having a molecular weight of about 230:Jeffamine™ T-403, a polyoxypropylene triamine having a molecular weightof about 400; and Jeffamine™ ED 600 and ED 900, which arepolyoxyethylene diamines having molecular weights of 600 and 900,respectively. In addition, hydrazino compounds such as adipicdihydrazide or ethylene dihydrazine can be used.

Sulfoarene- and sulfoalkanedicarboxylic acids of Formula VIII useful forpreparation of the water- and solvent-dispersible sulfocompounds of theinvention are any of the known sulfoarene- and sulfoalkanedicarboxylicacids. Examples of these include sulfoalkanedicarboxylic acids such assulfosuccinic acid, 2-sulfoglutaric acid, 3-sulfoglutaric acid and2-sulfododecanedioic acid; sulfoarenedicarboxylic acids such as5-sulfoisophthalic acid, 2-sulfoterephthalic acid,5-sulfonaphthalene-1,4-dicarboxylic acid; sulfobenzylmalonic acids suchas those described in U.S. Pat. No. 3,821,281; andsulfofluorenedicarboxylic acids such as9,9-di(2'-carboxyethyl)fluorene-2-sulfonic acid described in BritishPat. No. 1,006,579. It is to be understood that the corresponding loweralkyl esters, halides, anydrides, and salts of the above sulfonic acidscan also be used in the preparation.

2-Alkenylazlactones, compounds of Formula I, which can be caused toreact with sulfopolyols and sulfopolyamines to form theethenically-unsaturated compounds of the invention areethylenically-unsaturated compounds having a reactivity similar to theisocyanates for reaction with a nucleophilic group. Examples of

2-alkenylazlactones include 2-ethenyl-1,3-oxazolin-5-one,

2-isopropenyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-ethenyl-5,6-dihydro-5,5-dimethyl-4H-1,3-oxazin-6-one, and

2-isopropenyl-5,6-dihydro-5,5-dimethyl-4H-1,3-oxazin-6-one.

The reaction with the sulfopolyol is performed at 0° C. to 50° C. underatmospheric pressure in the presence of about 0.1 to 5 percent by weightof a Lewis acid such as BF₃ -etherate, AlCl₃, or SnCl₄, as catalyst. Thereaction with the sulfopolyamine is relatively rapid and is accompaniedby a mild exotherm and generally does not require a catalyst. Other2-alkenylazlactones and conditions that can be used are described inassignee's copending patent application Ser. No. 316,234, filed Oct. 29,1981, which is incorporated herein by reference.

Ethylenically-unsaturated isocyanates of Formula II useful in reactingwith the sulfopolyols or sulfopolyamines for preparing theethylenically-unsaturated sulfocompounds of the invention include2-isocyanatoethyl acrylate and methacrylate, 3-isocyanatopropyl acrylateand methacrylate, 2-acrylamidoethylisocyanate,3-acrylamidopropylisocyanate, 3-methacrylamidopropylisocyanate,2,3-bis(acryloyloxy)propylisocyanate3,3,3-tris(acryloyloxymethyl)propylisocyanate,4-methacryloyloxycyclohexylisocyanate,5-acryloyloxymethyl-3,3,5-trimethylcyclohexylisocyanate,allylisocyanate, methallylisocyanate, and the reaction product of thehydroxyalkyl acrylates and polyisocyanates given below.

Polyisocyanates, Formula III, that can be used to react with thesulfopolyols or sulfopolyamines to form the isocyanate-terminatedsulfopolyesters that are intermediates to the ethylenically-unsaturatedsulfocompounds of the invention are any of the well-knownpolyisocyanates. Preferred polyisocyanates are hexamethylenediisocyanate, toluene diisocyanate, isophorone diisocyanate,3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane,4,4'-diphenylmethane diisocyanate (MDI),4,4',4"-triisocyanatotriphenylmethane, and thepolymethylenepolyphenylisocyanates. Other polyisocyanates are well knownand include those described in U.S. Pat. Nos. 3,700,643 and 3,600,359among many others. Mixtures of polyisocyanates can also be used such asthe mixture of MDI and trimer of MDI available from Upjohn PolymerChemicals as Isonate® 1436 "Liquid MDI".

Ethylenically-unsaturated alcohols of Formula IV that can be used toreact with the isocyanate-terminated sulfopolyester in preparing theethylenically-unsaturated sulfocompounds of the invention are allyl andmethallyl alcohols, 2-hydroxyethyl acrylate and methacrylate,3-hydroxypropyl acrylate and methacrylate, 1,1,1-trimethylolpropanediacrylate, and dimethacrylate pentacrythritol triacrylate andtrimethacrylate. These compounds are well known and described in manypatents, such as for example, U.S. Pat. No. 4,108,840, col. 8, lines24-51. Especially preferred of these compounds are 2-hydroxyethylacrylate and 3-hydroxypropyl acrylate. Other preferred hydroxyalkylacrylates are 2,2,2-tris(acryloyloxymethyl)ethanol and2,3-di(acryloyloxy)propanol.

The ethylenically-unsaturated sulfocompounds of the invention can alsobe prepared by first reacting d moles of ethylenically-unsaturatedalcohols of Formula Iv, described above, with one mole of thepolyisocyanates of Formula III, also described above, and reacting thisethylenically-unsaturated isocyanate with the aliphatic polyol, (HO)_(c)R¹⁰ --OH, or aliphatic polyamine, (H₂ N)_(c) R¹⁰ --NH₂.

The coating composition of the invention may be prepared by dissolvingthe polymerizable ethylenically-unsaturated sulfocompound in a suitablesolvent. Water, aqueous-organic solvent, or an organic solvent can beused. Generally, from 0.05 to 20 parts, preferably 0.2 to 4 parts, ofsolvent, preferably water, are used per part ethylenically-unsaturatedsulfocompound. Examples of solvents that can be used include acetone,methyl ethyl ketone, methanol, aqueous methanol, aqueous ethanol,trichloroethylene, toluene, and the like. Other preferred solvents arethe reactive solvents that are ethylenically-unsaturated and arecopolymerizable with the ethylenically-unsaturated sulfocompound of theinvention. Particularly preferred reactive solvents are the acrylic andmethacrylic acid esters such as, for example, ethyl acrylate, butylacrylate, n-octyl acrylate, allyl acrylate, cyclohexyl acrylate,N-methylcarbamoyloxyethyl acrylate, neopentylglycol diacrylate,1,6-hexanediol diacrylate, pentaerythritol tetraacrylate,1,3,5-tri(2-acryloyloxyethyl)isocyanurate, and the correspondingmethacrylates.

Depending on the particular application of the coating composition itmay be desirable to include in the composition conventionalantioxidants, thermal stabilizers or free radical inhibitors in order toprolong storage life of the composition. Examples of such materials arebutylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT)commercially available as Ionox™ 220 (Shell), Santonox™ R (Monsanto),Irganox™ 1010 (Ciba-Geigy), etc. Generally, from 0.01 to 5.0 percent byweight of the total weight of the coating composition can be used.

The properties of the coatings can be further modified by including inthe coating composition a variety of adjuvants utilized for their knownpurpose, such as lubricants, plasticizers (e.g., dibutyl phthalate),tackifying resins (e.g., the copolymer of styrene andalpha-methylstyrene), inorganic thickeners, fillers (e.g., organic andinorganic particles, fibers, and flakes), pigments, and dyes. Fillerscan generally be used in proportions up to about 200 parts by weight per100 parts by weight of copolymerizable components of the coatingcomposition. When insoluble components are desired in the coatingcomposition, it may be necessary to use conventional high speeddispersing apparatus such as paint mills, ball mills, and the like.

Free radical generating compounds that can be used in the coatingcomposition of the invention for effecting the conversion, on exposureto energy, of coatings prepared from the composition havingethylenically-unsaturated terminal groups, from a solvent-soluble,hydrophilic state to a solvent-insoluble, hydrophobic state, arematerials known in the art. Particularly suitable free radicalgenerating compounds include, for example, organic peroxides, azocompounds, aromatic diazonium salts, aromatic iodonium salts, aromaticsulfonium salts, aromatic phosphonium salts, quinones, benzophenones,nitroso compounds, acyl halides, aryl halides, hydrazones, mercaptocompounds, pyrrylium compounds, triarylimidazoles, biimidazoles, andchloroalkyltriazines, These materials, in general, must havephotosensitizers therewith to form a photoinitiator system useful withradiation above about 400 nm. Photosensitizers, such as spectrallyabsorbing dyes, are well known in the art. Generally, the free radicalgenerating compound is used at a concentration of 0.01 to 10 percent,preferably 0.05 to 5 percent, by weight of the total weight of thecoating composition and the photosensitizer is used at a concentrationof 10 percent to 100 percent by weight of the weight of the free radicalgenerating compound.

Additional reference in the art to free radical photoinitiator systemsfor ethylenically-unsaturated compounds are included in U.S. Pat. No.3,887,450 (e.g., col. 4), U.S. Pat. No. 3,895,949 (e.g., col. 7), andU.S. Pat. No. 4,043,819. Preferred initiators are the onium salts asdisclosed in U.S. Pat. Nos. 3,729,313; 4,058,400 and 4,058,401. Otherdesirable initiators are biimidazoles (disclosed in U.S. Pat. No.4,090,877) and chloroalkyltriazines as disclosed in U.S. Pat. No.3,775,113. These references also disclose sensitizers therein. Anothergood reference to photoinitiator systems is Light-Sensitive Systems, J.Kosar, J. Wiley and Sons, Inc. (1965), especially Chapter 5.

The energy-curable compositions can be used to form crosslinked,adherent, abrasion-resistant coatings on substrates using substantiallyany technique known in the art including spraying, curtain coating,direct or reverse roll coating, dipping, brushing, extruding, andprinting. However applied, the coating is allowed to dry to removenon-copolymerizable solvent, where used, and leave a hard tack-freecoating that in the absence of applied energy, particularly actinic,remains soluble and can be removed from the substrate by treatment witha solvent, particularly water or an aqueous solvent such as aqueousmethanol. The dried coating can be crosslinked by exposure to radiationfor a sufficient time and intensity which may vary from about tenseconds to ten minutes or more depending on the thickness and particularcomposition of the coating.

Substrates which may be coated with the crosslinkable compositions ofthe invention include organic substrates of wood, fiberboard, particleboard, paper, and cardboard; synthetic and natural polymers such aspolyesters, polyamides, cured phenolics, urea-aldehyde resins,poly(vinyl halides), polyacrylates, polyurethanes, proteins, rubber;inorganic substrates such as iron, stainless steel, copper, brass,bronze, aluminum, titanium, nickel, zinc, and alloys. Particularlyuseful substrates are silicated aluminum and the polyesters such aspolyethyleneterephthalate and poly(vinyl chloride).

The energy-curable coatings of the invention can have a thicknessranging from about 0.01 m to about 10.0 mm or more, preferably 0.1 to1.0 mm.

Suitable radiation for use in the crosslinking the coatings of theinvention and rendering them insoluble include radiation at wavelengthsin the 200 to 600 nm range, preferably 200 to 450 nm. Suitable sourcesinclude sunlight, carbon arcs, mercury-vapor arcs, black light lamps,fluorescent lamps, argon and xenon glow lamps, electronic flash units,and photographic flood lamps. Electron accelerators and electron beamsources may also be used.

The energy-curable coating compositions of the invention, particularlywhen coated onto a substrate, are suitable for use in the graphic artsfor the recording of information, e.g., color separation images, inprinting plates and for use in the production of resist images, e.g.,printed circuits.

In addition to their use in the preparation of theethylenically-unsaturated sulfocompounds of the invention by reactionwith ethylenically-unsaturated alcohols, the isocyanate-terminatedsulfocompounds and their mixture with excess polyisocyanates are usefulfor the preparation of other sulfo group-containing polymers that arehydrophilic but insoluble in water. By reaction of theisocyanate-terminated sulfocompounds with water,sulfopolyoxyalkylenepolyureas and sulfopolyesterpolyureas are preparedthat are useful as hydrophilic coatings and self-supporting films. Byreaction with polyols, the isocyanate-terminated sulfocompounds formsulfopolyoxyalkylene-polyurethanes and sulfopolyesterpolyurethanes thatare also useful for preparation of hydrophilic coatings andself-supporting films. Polyols that can be used for the preparation ofthe hydrophilic polyurethanes are any of the polyols known to be usefulfor the preparation of polyurethanes. Preferred polyols are thealiphatic polyols, (HO)_(c) R¹⁰ OH disclosed above for the preparationof the sulfocompounds of the invention.

The isocyanate-terminated sulfocompound of Formula IX containing excesspolyisocyanate can be further reacted with (1) theethylenically-unsaturated alcohol of Formula Iv, or (2) the polyol orpolyamine of Formula X, or water, or hydrazino compounds such as adipicdihydrazide or 1,2-ethylene dihydrazine to provide, respectively, (1) amixture of the ethylenically-unsaturated sulfocompound of Formula VIIand an ethylenically-unsaturated compound not containing a sulfo group,and (2) a mixture of a sulfopolyurethane and a polyurethane notcontaining a sulfo group or a sulfopolyurea and a polyurea notcontaining a sulfo group. By varying the amount of excess isocyanatepresent in the composition the physical characteristics of the resultingmaterial can be controlled, e.g., hydrophilicity, tensile strength,hardness, etc.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention.

EXAMPLE 1 Illustrating the preparation of a sulfopolyester urethaneacrylate.

Into a one liter 3-neck flask equipped with a mechanical stirrer, refluxcondenser and drying tube, thermometer, and oil bath with temperaturecontrol, 130 g (0.1 mole) Sulfoester Polyol A (prepared as describedbelow), was added to 50 g (0.2 mole) bis(4-isocyanatophenyl)methane,0.03 g dibutyltin dilaurate, and 150 g methyl ethyl ketone. As stirringwas initiated, the temperature began to rise. Additional heat wasapplied to raise the temperature of the contents of the flask to 60° C.and held at this temperature until analysis indicated the disappearanceof hydroxyl and formation of isocyanate-terminated sulfopolyester (4hours). There was then added 65 g pentaerythritol triacrylate and 500ppm (with respect to the acrylate) of p-methoxy phenol. Stirring andheating was continued for an additional 4 hours at 60° C. The polymerwas readily soluble in water from which it could be coated as a film anddried to a non-tacky coating that could be redissolved in water, sodiumhydroxide solution, methanol, aqueous methanol, acetone, methylenechloride and other common organic solvents. The dried film had acalculated average molecular weight of 2400 and an acrylic groupequivalent weight of about 400.

A cleaned copper sheet was coated with a solution of 20 g of theabove-described carbamate acrylate of Sulfoester Polyol A (designatedCarbamate Acrylate I) and 0.2 g of benzoin ethyl ether in 80 ml of 20percent methyl ethyl ketone in water and dried in the air to provide acoating 5 micrometers thick. The film was exposed through a mask toultraviolet from a 20 watt black light lamp for 2 minutes. The unexposedareas were readily removed by presence of Urethane Acrylate I in exposedareas is readily detected by wiping the washed, exposed sheet with adilute solution of a cationic dye wherein the exposed areas take of theinvention as a resist material is illustrated by the fact that thecopper sheet bearing the water developed image is undamaged by immersioninto a Woods metal bath (this is a well known low temperature meltingalloy of bismuth and a mixture of other metals) at 260° C. for at least30 seconds, is undamaged by a refluxing bath of HCl containing methanol,and will withstand a 30 percent ferric chloride copper etching bathwithout undercutting.

Preparation of Sulfoester Polyol A

A one liter 3-neck flask was equipped with a mechanical stirrer, anitrogen purge, and set for vacuum distillation using a round-bottomflask which is cooled with a dry ice/acetone both for receivingdistillate. A Woods metal bath was used to heat the 3-neck flask. Intothe 3-neck flask was placed 148 g (0.5 mole) dimethyl5-sulfoisophthalate, 530 g PCP-0200 (1.0 mole of polycaprolactonediolhaving a weight average molecular weight of 530 available from UnionCarbide Corp.), 0.13 g tetraisopropyl titanate (0.02 percent by weight)as esterification catalyst. Nitrogen purge and agitation were initiated.The contents of the flask were brought to 230° C. and held for 4 hoursduring which time 50 to 75 percent of methanol condensate was removed.The pressure was reduced to 20 Torr and the temperature increased to250° C. and held for two hours. The system was then back filled withnitrogen and the low viscosity product removed from the flask while hot.It was found to have a hydroxyl equivalent weight of 650.

EXAMPLES 2-9

Ethenically-unsaturated carbamate esters of sulfoester polyols wereprepared by the procedure employed in EXAMPLE 1 using equivalent amountsof polyol and corresponding amounts of isocyanatoalkyl acrylates. Theparticular polyol and isocyanatoalkyl acrylate used to make theisocyanatoalkyl acrylate are given in TABLE 1. Also given in TABLE I arethe acrylic functionality and calculated acrylic equivalent weight ofeach urethane acrylate.

                                      TABLE I                                     __________________________________________________________________________                    Acrylic                                                       Ex.                                                                              Carbamate                                                                           Acrylic                                                                              equivalent                                                    no.                                                                              acrylate                                                                            functionality                                                                        weight                                                                              Polyol.sup.(a)                                                                           Isocyanatoalkyl acrylate                     __________________________________________________________________________    2  II    6      295   PCP ™ 0210.sup.(b)                                                                    TDI.sup.(c) /pentaerythritol                                                  triacrylate                                  3  III   6      260   Carbowax ™ 600.sup.(d)                                                                TDI/pentaerythritol triacrylate              4  IV    2      655   Polymeg ™ 1000.sup.(e)                                                                2-isocyanatoethyl methacrylate               5  V     2      230   trimethylene                                                                             2-isocyanatoethyl methacrylate                                     glycol                                                  6  VI    12     290   PCP ™ 0300.sup.(f)                                                                    MDI.sup.(g) /pentaerythritol                                                  triacrylate                                  7  VII   8      410   PCP ™ 0300                                                                            MDI/trimethylolpropane diacrylate            8  VIII  2      940   Polymeg ™ 650.sup.(h)                                                                 2-isocyanatoethyl methacrylate               9  IX    18     100   pentaerythritol                                                                          TDI/pentaerythritol triacylate               10 X     18     200   Jeffamine ™ D-400.sup.(i)                                                             TDI/pentaerythritol triacylate               __________________________________________________________________________     .sup.(a) the polyol from which the sulfoesterpolyol was prepared by           reaction of two moles of the listed polyol and one mole of dimethyl           5sulfoisophthalate                                                            .sup.(b) polycaprolactonediol having a molecular weight of 830 available      from Union Carbide Corp.                                                      .sup.(c) toluene diisocyanate, one mole of which was reacted with one mol     of pentaerythritol triacrylate to form the isocyanatoalkyl acrylate           .sup.(d) poly(oxyethylene)diol having a molecular weight of 600 available     from Union Carbide Corp.                                                      .sup.(e) poly(oxytetramethylene)diol having a molecular weight of 1000        available from Quaker Oats Co.                                                .sup.(f) polycaprolactonetriol having a molecular weight of 540 available     from Union Carbide Corp.                                                      .sup.(g) bis(4isocyanatophenyl)methane                                        .sup.(h) poly(oxytetramethylene)diol having a molecular weight of 650         available from Quaker Oats Co.                                                .sup.(i) polyoxypropylene triamine having a molecular weight of about 400

EXAMPLE 10

Coating compositions of each Carbamate Acrylate II-IX were prepared inaccordance with the procedure of EXAMPLE 1. To each composition wasadded 0.1 g of Methyl violet 2 B Base and the composition was coatedonto 75 m sheets of biaxially stretched poly(ethylene terephthalate) anddried in the air to provide a coating 5 micrometers thick. Each coatingwas exposed through a mask to ultraviolet light from a 20 watt blacklight at a distance of 8.9 cm (3.5 inches) for 5 minutes. The unexposedareas of the coating were readily removed by washing with water oraqueous methanol leaving a deep blue colored, tough abrasion-resistantcoating of insoluble polymer in the exposed areas.

EXAMPLE 11

A coating composition was prepared as described in EXAMPLE 1 and TABLE Ifrom 20 g Carbamate Acrylate II, 2.0 g poly(vinyl pyrrolidone) availablefrom GAF Corp., and 0.05 g Methyl violet 2B Base (as image indiator) in80 ml of 20 percent methyl ethyl ketone in water. 0.4 g of2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine (as disclosed inU.S. Pat. No. 3,954,475) was used as a photoinitiator. This compositionwas coated on grained anodized aluminum using a squeeze roll coater andthen dried. A coating weight of about 1.7 g per square meter wasobtained. The coating was exposed in a vacuum frame to a carbon arc for40 seconds through a neutral density filter and a negative. It wasdeveloped by wiping with aqueous methanol.

EXAMPLE 12

Using the procedure described in Example 1, two moles ofpolyoxyethylenediol having a molecular weight of 1000 and one mole ofdimethyl sodiosulfoisophthalate were caused to react and thesulfopolyoxyethylenediol obtained converted into theisocyanate-terminated sulfocompound by reaction with 1000 g (sevenisocyanate equivalents) of Isonate® 143L in accordance with theprocedure also described in Example 1. The products obtained was anisocyanated-terminated sulfocompound having an isocyanate equivalentweight of about 450.

The isocyanate-terminated sulfocompound was converted to theethylenically-unsaturated sulfocompound by heating 45 grams with 37.1grams of pentaerythitol triacrylate in accordance with the proceduredescribed in Example 1. The polymer obtained was readily soluble incommon solvents from which it could be coated as a film that dried to anon-tacky coating that could be redissolved in common solvents.

A cleaned copper sheet was coated with a benzoin ethyl ether-sensitizedsolution of the above described ethylenically-unsaturated sulfocompound,dried, exposed and developed as described in Example 1. The exposedareas were undamaged when the copper sheet was immersed in a Woods metalbath at 260° C. for 30 seconds and withstood a 30 percent ferricchloride copper etching bath without undercutting.

The above described isocyanate-terminated sulfocompound was moisturecured on a Teflon® coated spin caster using the moisture in the ambientair (about 50% relative humidity). A rubbery tack-free film about 40micrometers in thickness was obtained. The film had a tensile strengthat break of 17.5 megapascals (MPa) and an elongation of 350% at 50% RHand a glass transition temperature (Tg) of -6° C. The film washydrophilic and gained 75% in weight when placed in water. On drying,the film returned to its original characteristics.

EXAMPLE 13

The procedure of Example 12 was repeated using four moles instead of twomoles of polyoxyethylenediol 1000 and 15 instead of 7 isocyanateequivalents of Isonate® 143L. Similar thermal and undercutting resultswere obtained for cured coats of the cured isocyanate-terminatedsulfocompound on copper sheeting as was obtained for the coating inExample 12.

When cured on the spin caster as described in Example 12, a rubberytack-free film was obtained having a tensile strength at break of 10.9MPa and an elongation of 250% at 50% RH and a glass transitiontemperature of --6° C.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention, and it should be understood that thisinvention is not to be unduly limited to the illustrative embodimentsset forth herein.

I claim:
 1. A sulfopolyurea or a sulfopolyurethane prepared by thereaction of a compound selected from the group consisting of water, ahydrazino compound, and a polyol or polyamine having the formula HXR¹⁰(XH)_(c), with an isocyanate-termined sulfopolyester or sulfopolyamidehaving the formula ##STR20## wherein R⁹ is an arenetriyl (trivalentarene) group having 6 to 12 carbon atoms or an alkanetriyl (trivalentalkane) group having 2 to 12 carbon atoms remaining after the remodel ofcarboxyl and sulfo groups from sulfoarene- and sulfoalkane dicarboxylicacids having the formula ##STR21## in which M is a cation, or a primary,secondary, tertiary, or quaternary ammonium cation, andbenzyltrimethylammonium cation;R¹⁰ is a linear aliphatic group having avalence of (c+1) consisting of a saturated chain of up to about 110carbon atoms in units of 2 to 12 --CH₂ -- groups which can be separatedby individual oxygen atoms and ##STR22## the aliphatic group having amolecular weight of up to about 2000, wherein c is an integer of 1, 2,or 3; R¹² is an organic group having a valence of (d+1) selected fromlinear and branched groups having 2 to 12 carbon atoms, 5- and6-membered carbocyclic groups having 5 to 14 carbon atoms wherein d isan integer having a value of 1 to 3; and X is --O-- or --NH--.
 2. Thesulfopolyurea or sulfopolyurethane according to claim 1 which is acoating on a substrate.
 3. The sulfopolyurea or sulfopolyurethaneaccording to claim 1 which is a self-supporting film.
 4. Thesulfopolyurea or sulfopolyurethane according to claim 1 wherein saidreacting compound is water.
 5. The sulfopolyurea or sulfopolyurethaneaccording to claim 1 wherein said reacting compound is a hydrazinocompound.
 6. The sulfopolyurea or sulfopolyurethane according to claim 1wherein said reacting compound is a polyol.
 7. The sulfopolyurea orsulfopolyurethane according to claim 1 wherein said reacting compound isa polyamine.
 8. The sulfopolyurea or sulfopolyurethane according toclaim 4 which is a self-supporting film.
 9. The sulfopolyurea orsulfopolyurethane according to claim 6 which is a self-supporting film.10. The sulfopolyurea or sulfopolyurethane according to claim 5 whereinsaid hydrazino compound is adipic dihydrazide.
 11. The sulfopolyurea orsulfopolyurethane according to claim 5 wherein said hydrazino compoundis 1,2-ethylene dihydrazine.
 12. The sulfopolyurea or sulfopolyurethaneaccording to claim 6 wherein said polyol is a polyoxyalkylene diol. 13.The sulfopolyurea or sulfopolyurethane according to claim 6 wherein saidpolyol is a polyester diol.
 14. The sulfopolyurea or sulfopolyurethaneaccording to claim 6 wherein said polyol is a polylactone diol.
 15. Thesulfopolyurea or sulfopolyurethane according to claim 7 wherein saidpolyamine is a polyoxypropylene diamine.
 16. Asulfopolyoxyalkylenepolyurethane and sulfopolyethane prepared by thereaction of an isocyanate-terminated sulfopolyester or sulfopolyamidehaving the formula ##STR23## wherein R⁹ is an arenetriyl (trivalentarene) group having 6 to 12 carbon atoms or an alkanetriyl (trivalentalkane) group having 2 to 12 carbon atoms remaining after the removal ofcarboxyl and sulfo groups from sulfoarene- and sulfoalkane dicarboxylicacids having the formula ##STR24## in which M is a cation, or a primary,secondary, tertiary, or quaternary ammonium cation, andbenzyltrimethylammonium cation;R¹⁰ is a linear aliphatic group having avalence of (c+1) consisting of a saturated chain of up to about 110carbon atoms in units of 2 to 12 --CH₂ -- groups which can be separatedby individual oxygen atoms and ##STR25## the aliphatic group having amolecular weight of up to about 2000, wherein c is an integer of 1, 2,or 3; R¹² is an organic group having a valence of (d+1) selected fromlinear and branched groups having 2 to 12 carbon atoms, 5- and6-membered carbocyclic groups having 5 to 14 carbon atoms wherein d isan integer having a value of 1 to 3; and X is --O-- or --NH--,with apolyether or polyester polyol or polyamine having the formula

    HXR.sup.10 (XH).sub.c

wherein X and R¹⁰ are previously defined.